Phthalocyanine derivatives



No Drawing. Appliationfliilyi 14, I953 Serial No. 367,986

. This invention'relates :to :novel icornpounds of the aphthalocyahineseries.

The compounds of this invention I'IHIG'IIOVEI phthalocyan'inederivatives which maybe Fdescribed' aszphthalocya'nines containing atleast one: mthy1ene-2,'4'-'dihydro3ry- S-carboxybenzene redicalnuclearly attachedfthrough' the methylene groups to an arylradicaltherein, i. e., (1) to a phenylene nucleusof the fundamentalphthalocyanine nucleus or (2) to a pendant aryl nucleusattached directlyor through abridging link to a phenylenenucleus'of'the fundamentalphthalocyanine nucleus. Such compounds have the following formula:

CODE 7:

in which P-cy represents a fundamental phthalocyam'ne nucleus, A is a Igroup of the formula:

D is a divalent bridging link, q has-a value'rof *or--1,.Ar representsapendant-aryl nucleus comprising 'noniore than 10 cyclic carbon atoms, mhas=a value of-0 toa8, R1 is selected from the group consisting ofhydrogen and inert substituents such as loweralkyl, lower alkoxy and thelike, and n has a value of at least'one.

The compounds of this inventionxmay-be produced by reactingaphthalocyanine compound containingmt least one chloromethyl group witha ,s-resorcylic acid compound of the formula:

I l "R1 COOH in which R1 has the values given-above. Compoundscorresponding to the latter formulaare fi-resorcylic acid and itsindicated methyl, ethyl, methoxy and/ or ethoxy substituted derivatives,and the like.

Thereaction involved in the process according to the instant inventionmaybe depicted as follows:

l COOH in which the various characters have the values given above.

ice

2 flThelphthalocyani-ne nucleus (Pcy) in the above-iormula may.beiderivedlfrom a metal: free plrthal'ocyanine or'from a metallic:phthalocyanine such as copper phthalocyanine,

zinc :phthalocyanine, :aluminurn .tphthalocyan'ine, :tin

5 phthalocyanine, manganese1phthalocyanine, nickeltphthaliocyanine,"iron :phthalocyanineand the like.

Examples of "monoatomic tor adiatomic bridging links (D) in f the aboveeformnila: by which: the 2 pendant :aryl nucleus .(Ar) "in thez'fonmulaJmay .zbenattached to the lphthalocyanine "nucleus are S, -'O, CO-,'-S0z, CH'2S'-,- -@H2SO2-+.;.CH2O, -GHzCO-', :SOzCHa-, ZSO2NR., -'NRCO,-NRS2, .SO2O, and the like, wherein R'zstands-fonhydrogen or ahydrocarbon"radicalvsuchr'asfmethyl-, 'thyl and the like. "The pendant.arylinucleusi (Ar)amay'beibenzene'rori naphathalene,wunsubstituted orsubstituted-by: lower alkyl 'ra'diucals such as :methylaaudf or :ethyl.:.-l2hthalocyanine iderivativescontaining suchupendant aryl nucleiand'their rmethods of tmanufacturezare. persei knownt and no claims theretotare made herein.

Theirphthal'ocyanine :precursors of the compounds :of :the instant'iil'lVElltlOIl, :unsubstituted or substituted by pendant arylnuclei,imay :becchloromethylated in known mannergsaslfor example:iaccoriding'r t'o'the: procedures dis- 2 zclosed an -U. vs. Patents2,435,307, 2,542,327 and ..2;5 423:28,':for'zexampleirbytcondensation ofthe ph'thalo- *icyanine at elevated temperatureszin thepresence ofalumiitiurn chloride and ipreierablyt of/a' tertiary :amine: Lno'ti sus-0 1ceptible' to.chloromethylationpwithfsymmetrical bichloro-"rnethyIFether or'sa reactant such asiparaformaldehyde which crr'eactslike bischloromethyl:ether'in thepresenceiofraluminumlchloridesfiritheiihthalocyaninerprecursorLmayJbe'zchloromethylatedcby reactionwithibischloromethylx ether rinntherpresence: of sulfuric' acidtor'vmethyl. hydrogen; sulfate, "or:in otheriknownrmanner.

Representative :of chloromethylated :unsubstituted fphthalocyanine.'compoundsxuseful. as starting materialsr'inithel'produc'tion'rof the compounds :of theinsta'nt. invention 0 J are:-metal-- and vrnetal=free:mono-,Edit,itri fitetraq: penta-,:hexa-;hepta-, andso'cta-- (chloromethyl)aphthalocyanines. In' thesecompounds no more :'-than two ichloromethyl groups J. are inuclearlyattached to any i'orie i'phenyle'ne "nucleus ofthefundamentalplithalocyanine.:nucleus. 5 Where tthe, plithalocyanine z'startin'g:materialcontains one or Lrnore pendant-iaryl" :nuclei attached:directly ::or throughiaalinking atom for: group: of atomstoia'iphenylene fnucleus :of the fundamental:phthalocyaninemucleus,s thechloromet-hylation-z'step introduces .chloromethyl groups 'into-ithearylvresidues ofthe: pendant-aryl nuclei. '"iInigeneral,--no more; thantwo pendant arylinu'clei may be \int'ro- 'duced into :"any lonewofithefour phenylene snuelei' of .the "fundamental phthalocyanine'nucleusgior; a maximum .of S r-pendant :arylnuclei (m 'inthesaboveifoimula) and" no more. than 'two' 'chloroinethyl zgroups'rmaybe introduced into anyfonezof' therpendant' aryl- 'nuclei, forarrnaximumof 16 chloromethylisgroups (riin the above formula).

".In thCiPlOCCSS of ithe instantiinvention in whi ch thechloromethylated."phthalo'cyanine" startingrmaterlal: isrreacted withthe fi resorcylic acidtcompoundyacondensation takes place betweenthereactants involving liberation of hydrogen chloride. The reaction may becarried out by the application of heat with or without the assistance ofa catalytic substance. In general, the reaction may be carried out attemperatures rangingfrom aboutl00"to C. Theoretically, the, B-resorcylicacid compound should be employed in an amount at least equivalent to thechlorine contained in the chloromethyl groups of the phthalocyaninecompound. However, the reaction may be carried out in the-presence of anexcess of the ,B-resorcylic acid compound, which thus acts as both areactant and a solvent or diluent. The use of a catalyst enables outimpurities.

the reaction to proceed at somewhat lower temperatures within theaforementioned range. In general, suitable catalysts are metallichalides such as stannic chloride, ferric chloride, aluminum chloride,zinc chloride, mercuric chloride, and the like. Where a catalyst isemployed, the reaction is preferably carried out in the presence of aninert reaction medium such as naphthalene, nitrobenzene,dichlorobenzene, and the like, in which case only a slight excess of thefl-resorcyclic acid compound over that theoretically required need beemployed. The reaction may also be carried out in a fused melt medium,as for example, molten sodium chloride and the like.

'The duration of the reaction is of course variable depending upon thetemperature employed, reactants involved, and the like, completion ofthe reaction being indicated by cessation of the evolution of hydrogenchloride. reaction mixture by pouring into water and filtering andpurifying the precipitated product of the invention. When the reactionis carried out in a hot melt such as fused salts, the mass may beallowed to cool and harden after completion of the reaction, and themass then pulverized and treated with an acidic In some cases excessfi-resorcylic acid compound may, after completion of the reaction, beremoved by extraction or steam distillation.

The products of this invention have highly desirable properties. Theypossess excellent light fastness and are useful for coloring ureaformaldehyde resins, nitrocellulose lacquers, spirit varnishes and thelike. They exhibit excellent solubility properties in dilute alkaliwhich, when coupled with the improved lightfastness, render them usefulas colors in alkali soluble inks and the like. The

- fact that they are insoluble in hydrocarbon solvents but soluble inspirit solvents renders them of value as dyestutls for certain fabricswhich are subjected to dry cleaning fluids. ish-blue to greenish-yellow.Those products of the invention are particularly effective which containat least 4 pendant aryl nuclei joined to the phenylene nuclei of thefundamental phthalocyanine nucleus through a bridging link and from 1.5to 2 methylene-2,4-dihydroxy-5-carboxybenzene radicals nuclearlyattached to each of the pendant aryl nuclei (q=l, m=4 to 8, and n=6 to16in the above formula). These preferred products have highly desirablespiritand alkali-solubility characteristics. It will of course beunderstood that the products of this invention may also be employed asintermediates in the manufacture of other derivatives. For example, the

ortho-hydroxy-carboxy structure of the products renders them highlysuitable in the preparation of lakes.

Reference is herewith made to U. S. Patents 2,430,052,

2,124,299 and British Patents 589,118 aud'565,200 for disclosures ofphthalocyanine starting compounds use ful in the process of thisinvention, including those containing pendant aryl nuclei attacheddirectly or through a linking atom or' group of atom to phenylene nucleiof the fundamental phthalocyanine nucleus.

The following examples in which parts are by weight unless otherwiseindicated are illustrative of the instant invention and are not beregarded as limitative.

I" OH OuPcy- OH on The resulting product maybe separated from the v To amixture of 31 g. of p-resorcylic acid, 200 ml. of dry nitrobenzene and 8ml. of anhydrous stannic chloride were added 8 g. of coppertetrachloromethylphthalocyanine. The reaction mixture was mechanicallystirred and heated slowly to 115 C. Then the heating period wascontinued at l15-120 C. for six hour When cool, the crude product wasisolated by diluting the reaction mixture with benzene, collecting theprecipitated solid on a filter, washing first with benzene, then lowboiling petroleum ether and finally water. It was purified by solutionin 500 ml. of 2% sodium hydroxide, filtering, neutralizing the filtratewith hydrochloric acid, collecting the product on a filter, washing anddrying to yield 14 g. of bluish-green solid. It is an alkaliandspirit-soluble dye possessing good lightfastness.

Example ll The procedure of Example I was repeated except that 8.5 g. ofcopper trichloromethylphthalocyanine were employed instead of the coppertetrachloromethylphthalocyanine. The reaction product was found toexhibit very aqueous solution todissolve similar properties. However,the shade was shifted slightly toward the blue.

; Example III F OH 0 P o n cy LS 0 0H m 00H (luPoy sovqOHa on v H OH+HC1 The products range in color from green- 10 g. of coppertetra-(x-chloromethy1-4-to1ylsulfonyl)- phthalocyanine (U. S. P.2,542,328, Example 4) were added to a mixture of 28 g. of fl-resorcylicacid, 200 ml. of dry nitrobenzene and 8 ml. of anhydrous stannicchloride. The reaction was carried out as in Example I. The productproved to be a greenish-blue, alkaliand spirit-soluble dyestuff.

Example IV CHzOl OH CuPcy-S GH; 8 0H -s L GHtOl 4 OOH OH OH CuPey-S OH;OCH

H: OH

GOOH 4 The process of Example III was repeated except that thephthalocyanine starting compound was substituted by 10 g. of coppertetra-(bis-x,x-chloromethyl-4-tolylmercapto)-phthalocyanine prepared byreaction of 8 moles of bischloromethyl ether with 1 mole of coppertetra-4-(ptolylmercapto) -phthalocyanine (U. S. 2,456,274). Theresulting greenish product was found to exhibit excellent ""spirib,ketoneand alkali-solubility It is to be understood that equivalentamounts of chloromethylated phthalocyanine derivatives, in which thependant aryl nuclei are attached to phenylene nuclei of the fundamentalphthalocyanine nucleus through any of the divalent bridging links D"described hereinabove other than the -SOzlinkage of Example 111' and theS linkage of Example IV, may be substituted for the startingchloromethylated phthalocyanine derivatives of Examples 111 and IV inorder to produce the corresponding products of the instant invention.

Various other modifications and variations of this invention will beobvious to a person skilled in the art and it is to be understood thatsuch modifications and variations are to be included within the purviewof this application and the spirit and scope of the appended claims.

We claim:

1. A compound of the formula aid 1.. OH 0.

Lil

in which Pcy represents a fundamental phthalocyanine nucleus, A is agroup of the formula:

D is a divalent bridging link selected from the group consisting of -S-,O, CO, -SO2-, CH2S, CH2SO2, CH20, CH2CO-, SO2CH2, SO2NR, NRCO, NRSO2-and SOzO- wherein R is a member of the group consisting of hydrogen andlower alkyl, q has a value of or 1, Ar represents a pendant aryl nucleusselected from the group consisting of benzene and naphthalene, m has avalue of 0 to 8, R1 is selected from the group consisting of hydrogen,lower alkyl and lower alkoxy, and n has a value of at least one.

2. A compound as defined in claim 1 containing a copper phthalocyaninenucleus.

3. A compound as defined in claim 2 in which Ri is hydrogen.

4. A compound of the formula OuPcy-CH OOOH 4 in which CuPcy is copperphthalocyanine.

5. A compound of the formula I COOH 3 in which CuPcy is copperphthalocyanine.

6. A compound of the formula CuPey- SO CHs O H OOH 4 in which CuPcy iscopper phthalocyanine.

LE O].

( JOOH 4 in which CuPcy is copper phthalocyanine.

8. A process comprising reacting by heating a compound of the formulawith n molecular equivalents of a compound of the formula I ll OOH inwhich Pcy represents a fundamental phthalocyanine nucleus, A is a groupof the formula:

D is a divalent bridging link selected from the group consisting of S,O-, CO, SO2-, CH2S, CH2SO2--, CH2O, CH2CO, SO2CH2-, SO2NR, NRCO, NRSO2and SOzO- wherein R is a member of the group consisting of hydrogen andlower alkyl, q has a value of 0 or 1, Ar represents a pendant arylnucleus selected from the group consisting of benzene and naphthalene,in has a value of 0 to 8, R1 is selected from the group consisting ofhydrogen, lower alkyl and lower alkoxy, and n has a value of at leastone.

9. A process as defined in claim 8 containing a copper phthalocyaninenucleus.

10. A process as defined in claim 9 in which R1 is hydrogen.

References Cited in the file of this patent UNITED STATES PATENTS2,124,299. Holyzach et al July 19, 1938 2,435,307 Haddock et al. Feb. 3,1948 2,604,476 Jones July 22, 1952 2,706,199 Brentano Apr. 12, 1955

1. A COMPOUND OF THE FORMULA